Silicon Nitride Ceramic For All-Ceramic Dental Restorations
Silicon Nitride Ceramic For All-Ceramic Dental Restorations
Silicon Nitride Ceramic For All-Ceramic Dental Restorations
1
Department of Prosthodontics, Ankara Yıldırım Beyazıt University, Ankara, Turkey
2
Department of Biomedical Engineering, Ankara Yıldırım Beyazıt University, Ankara, Turkey
3
Department of Basic Sciences School of Dentistry, Ankara Yıldırım Beyazıt University, Ankara, Turkey
4
Department of Metallurgical and Materials Engineering, Bilecik Şeyh Edebali University, Bilecik, Turkey
5
Department of Metallurgical and Materials Engineering, Ankara Yıldırım Beyazıt University, Ankara, Turkey
Corresponding author, Mahmut Sertaç ÖZDOĞAN; E-mail: msozdogan@ybu.edu.tr
Silicon nitride (Si3N4) is one of the promising ceramics for dental restoration due to providing significant benefits during the application.
This study aimed to investigate the potential use of Si3N4 for all-ceramic dental restorations by characterizing some critical properties
as color shade, mechanical resistance, shear-bond strength and radiolucency. For our study, porous Si3N4 ceramic was produced by
partial sintering process with limited amounts of sintering additives and low temperature. A commercial ZrO2 ceramic was prepared
according to manufacturer’s instructions and results were compared with Si3N4. Si3N4 is an attractive ceramic for dental applications
with good mechanical properties even in porous form, it has additional advantages over the conventional ceramics used as restorative
material, such as, inherent antibacterial/anti-infective activity, radiolucency, and lower hardness. It is expected that Si3N4 will
become popular in dental applications as well.
by various factors, such as, type and oxidation state of 3. Physical and mechanical characterization of samples
the rare-earth additives, impurities, grain boundaries Open porosity and bulk density values of samples
and porosity. Dense Si3N4 ceramics are considered too were determined by Archimedes’ displacement
dark colored for especially restorative applications. method according to ASTM C-20 standards21). Pore
However, lighter colors, suitable for dental applications, size distribution was measured by mercury intrusion
can be obtained when open porosity is introduced into porosimetry (MIP) (Autopore IV, Micromeritics,
Si3N4 ceramics20). Norcross, GA, USA).
This work aims to investigate some critical properties X-ray diffraction (XRD) was performed for phase
of Si3N4 for possible restorative applications. Si3N4 analysis using monochromatic Cu-Kα radiation
ceramic were produced via partial sintering, thus some (λ=1.5406 Å) (Rigaku MiniFlex-600, Tokyo, Japan). The
amount of open porosity was formed within samples. microstructure was investigated by scanning electron
Physical, mechanical, adhesive, optical and radiolucency microscopy (SEM) (Hitachi SU5000, Tokyo, Japan) from
properties of the produced ceramics were characterized the fracture surface of samples.
and compared with a commercial ZrO2 dental ceramic. Mechanical characterization of samples was done
according to ASTM C1161-18 standards22). Using ten
MATERIALS AND METHODS specimens with 3×4×50 mm dimensions, three-point
flexural strength and elastic modulus measurements
Preparation of samples were done. Bending load was applied using a universal
1. Fabrication of Si3N4 samples testing machine (Instron 5581, Backinghamshire, UK)
Si3N4 ceramics were prepared using α-Si3N4 powder (SN- at a cross-head speed of 0.5 mm/min with a support
E-10, Ube Industries, Yamaguchi, Japan) by adding span of 40 mm. Due to the porosity of Si3N4 samples,
2.50 wt% Y2O3 (Grade C, H.C. Starck, Selb, Germany) no grinding and polishing steps were applied for bar
and 2.50 wt% CeO2 (Inframat, Manchester, CT, USA) as specimens. Hardness measurements were performed by
sintering additives. Uniaxial dry pressing was used for Vickers indenter (Shimadzu HMV-G, Kyoto, Japan) at
shaping the samples. load of 98 N for 10 s.
For three-point flexural test, bar-shaped samples
were prepared according to ISO 14704:2000. For Color shade measurement
radiography and color shade measurement tests, disk- Color shade measurements were performed between
shaped samples with a diameter of 10 mm and 0.50, 1.00 400–700 nm with a clinical spectrophotometer (VITA
and 1.50 mm thickness were prepared (n=10 for each Easyshade V, VITA Zahnfabrik, Bad Säckingen,
thickness). Germany) with a probe tip of 5 mm. Illumination of
For shear bond strength (SBS) test, 5×5×5 mm the specimen was provided by the LED light from the
cubic samples were prepared. All samples were sintered periphery of the tip into the specimen surface. The
by pressureless sintering in a graphite furnace (FCT display of the spectrophotometer shows the closest VITA
Anlagenbau, Germany) at 1,700°C for 1 h under N2 shade in the VITA Classical shade guide from A1 to D4.
atmosphere. The samples were photographed with Vita Classical A1-
D4 Shade Guide under naturel daylight.
2. Fabrication of ZrO2 samples
For radiography and color shade measurement tests, Shear-bond strength measurement
disk-shaped samples with a diameter of 10 mm and The SBS measurements were done on extracted caries
0.50, 1.00 and 1.50 mm thickness were prepared (n=10 free third molars. The protocol was approved by the
for each thickness). Ethics Committee of the Ankara Yıldırım Beyazıt
For SBS test, 3×3×3 mm cubic specimens were University, under the protocol number 29.05.2019/40.
prepared. All ZrO2 samples were prepared from Twenty caries free third molars were collected
commercially available pre-sintered ZrO2 discs (Zirking, at the Tepebasi Oral and Dental Health Hospital of
Huge Dental, Shandong, China) using a CAD-CAM Ankara Yıldırım Beyazıt University, Turkey. Collected
device (CAD; Dental Wings Open System, DWOS, teeth were kept in 0.5% Chloramine T (Explicit
Montréal, Canada, CAM: Yenadent D40 CAM, ZenoTec, Chemicals, Pune, India) at 4oC until the time of use.
Istanbul, Turkey). ZrO2 specimens were sintered in a The teeth were cut in mesiodistal direction just above
high-temperature furnace (Protherm MoS-B 150/1, Alser the cementoenamel junction using a Micracut 201
Teknik, Ankara, Turkey) for 2 h at 1,375°C. automated precision cutting machine with water cooling
Both Si3N4 and ZrO2 samples were airborne- (Metkon, Bursa, Turkey) to expose a flat dentin. The
particle abraded with 50 μm Al2O3 particles (BEGO exposed dentin surfaces were visually investigated to
Korox, Bremen, Germany) applied perpendicular to the ensure the absence of residual enamel and exposure
specimen surface at 0.28 MPa pressure, from 10 mm of the pulp. Teeth with residual enamel were further
distance for 20 s. All specimens (except for Si3N4 bars) ground down until flat dentin surfaces were achieved.
were polished using 800-grit silicon carbide (SiC) paper Teeth with exposed pulp were not used. The teeth were
(Struers, Willich, Germany). then embedded in self-curing dental acrylic (IMICRYL
Cold cure, Konya, Turkey) up to a few millimeters below
the sectioned surface with the aid of a plastic mold.
1082 Dent Mater J 2020; 39(6): 1080–1086
The prepared specimens were randomly assigned placed on a photostimulable phosphor (PSP) imaging
into three groups (n=10 for each group). In group 1 Si3N4 plate (ScanX; Air Techniques, Melville, NY, USA). A
cubes were first treated with a silane coupling agent 99% pure graduated aluminum step wedge, thickness
(Ultradent, South Jordan, UT, USA) for 2 min and then ranging from 1 to 11 mm was also placed on the PSP
luted to dentin. In group 2 and 3 Si3N4 and ZrO2 cubes imaging plate as control. Radiographs were taken using
were luted to dentin directly, without pretreatment with a dental X-ray unit (Villa Sistemi Medicali, Buccinasco,
a coupling agent. Panavia Cement SA Plus (Kuraray Italy) maintaining the X-ray beam perpendicular to the
Noritake Dental, Tokyo, Japan) was used as adhesive specimens at 70 peak kilovoltage (kVp), 0.32 s exposure
in all groups. Each cube was luted under 1 kg fixed and 7 mA current23). The radiographs were saved as TIFF
pressure and light-cured for 20 s from four sides (5 s×4 files. The radiodensity (average pixel intensity) of the
sides) using an LED lamp (Linuo, Yunnan, China) with samples were determined using ImageJ software v1.52a
a light output of not less than 800 mW/cm2. (National Institute of Health, Bethesda, MD, USA) by
The cemented specimens were subjected to thermal selecting a region on the image and measuring the pixel
cycling alternating between 5oC and 55oC for 72 h intensity value. First the radiodensity of each step on
using an automated thermal cycler (THE-1100, SD the aluminum step wedge was measured. Then the
Mechatronik, Feldkirchen-Westerham, Germany). intensity of each disk was measured and the thickness
Following the thermal cycling, shear strength vs. radiodensity values were plotted for the Si3N4, ZrO2
measurements were performed using a universal testing and Al specimens. Kruskal-Wallis and Tukey multiple
machine (Lloyd LRX, Ametek, Berwyn, PA, USA). A comparison tests (α=0.05) were used for statistical
force parallel to the sectioned surface was applied at analysis.
the base of the cubes with 1 mm/min cross-head speed
until fracture. One-way ANOVA (α=0.05) was used for RESULTS
statistical analysis of the SBS measurements.
Densification and phase development of Si3N4 and ZrO2
Radiopacity measurement samples
Disk shaped Si3N4 and ZrO2 specimens with thickness The porosity and pore characteristics of Si3N4 and ZrO2
values of 0.50, 1.00 and 1.50 mm (n=10 for each group) are listed in Table 1. Partial sintering (by using limited
were prepared for radiopacity measurements. Each sintering additives and lower sintering temperature)
disk was numbered, and the thickness of each disk was enabled formation of porous Si3N4. Relative densities
determined using a digital caliper. The disks were then of Si3N4 and ZrO2 were measured as 84.12 and 99.23%,
Fig. 1 SEM images of the produced Si3N4 ceramic under (a) 5,000× and (b) 15,000× magnification and (c) XRD
patterns of Si3N4 and ZrO2 (β: β-Si3N4, Y: Y2SiO4, Z: t-ZrO2).
Table 1 Physical and mechanical properties of the Si3N4 and ZrO2 ceramics used in the study. (Average±standard deviation)
respectively. The open porosity of Si3N4 was 10.54% samples were determined as C4 and A1, respectively, for
where nearly no open porosity was measured for ZrO2. all thicknesses. Even though the shade of Si3N4 was in
Rod-like β-Si3N4 grains with various thicknesses the darker range of the guide, the color is acceptable for
were developed in the structure as seen in Figs. 1a and the restorative dental applications24,25).
b. The presence of porosity shows that the densification
was successfully controlled by partial sintering. The
micron-size pore was compatible with the size of pore
that was measured by MIP. Also, strong neck formation
was observed (Fig. 1b), that contributes to the mechanical
resistance of the ceramic.
XRD analysis showed that the produced ceramic
contains β-Si3N4 as the major phase and Y2SiO4 has
been formed by the reaction between Y2O3 and SiO2 (the
passive oxide layer of Si3N4) as the secondary phase
(Fig. 1c). t-ZrO2 was detected as the only phase in ZrO2
ceramic.
Table 2 L*, a* and b* values for ZrO2 and Si3N4 at different thicknesses. (Average±standard deviation)
Thickness (mm)
Adhesive failure
Sample Cohesive failure Mixed failure
Dentin-cement Ceramic-cement
ZrO2 4 1 1 4
Si3N4 1 8 — 1
Si3N4+silane 5 1 2 2
Fig. 4 (a) Radiographs and (b) radiodensity values of the Al, ZrO2 and Si3N4
specimens.
a, b, c, d: no statistically significant difference (p>0.05).
sintering stage. Substantial changes observed in grains limits the use of dense Si3N4 as a restorative material.
as the volume fraction of liquid (generally 2–5 vol%) is However, due to the porous nature of the Si3N4 produced
limited, a flat shape is developed in the contact regions of in this study, suitable shade (C4) for restorative use was
surrounding grains28). The flat tip of grains formed sharp- obtained.
edged pore shape as seen in Figs. 1a and b. During the
partial sintering, particles of powder compact are bonded Shear-bond strength evaluation
either via surface diffusion or evaporation–condensation A significant difference in SBS was observed between
processes. A strong neck formation was observed. the Si3N4 ceramics luted to dentin with and without
a silane coupling agent pre-treatment. The adhesive
Mechanical characterization system used in this study, Panavia Cement SA, is an
Glass ceramics, glass infiltrated ceramics, polycrystalline MDP monomer containing adhesive. This monomer has
Al2O3 and ZrO2 have been used in all ceramic dental an M-R-X structure, where M is a metacryl group, R is
restorations as core materials. Depending on the type the carbon chain and X is an acidic phosphate group.
of ceramic, flexural strength ranges from 150 to 1,500 Acidic phosphate reacts with the metal oxides, such as
MPa29). None of these core materials contain porosity and ZrO2, Al2O334). Since Si3N4 is thermodynamically unstable
the flexural strength depends on the intrinsic behavior of under oxidative conditions, its surface is always covered
each ceramic. Porosity is one of the flaws that results in with a 3 to 5 nm thick oxide layer7). Due to this oxide
stress concentration, and hence, reduces the strength in layer, Panavia Cement SA could not form a chemical
ceramics30). Since Si3N4 bars were tested in as-fabricated bond with the Si3N4. For silica based ceramics, a silane
form (i.e., without polishing), higher standard deviation coupling agent can be used between the ceramic and
was observed in the flexural strength measurements. adhesive material35). As silane molecules are activated,
Despite its porous nature, Si3N4 had moderate flexural methoxy (-OCH3) groups are replaced by hydroxyl (-OH)
strength compare to their dense counterparts. The strong groups and they directly react with the hydroxyl groups
neck formation between β-Si3N4 grains, the intertwined that exist on the surface and covalent bonds are formed
distribution of these grains and crack deflection via a condensation reaction36). This explains the effect of
potential of rod-like β-Si3N4 are the reasons for observed silane coupling agent on the SBS of Si3N4.
moderate strength of porous Si3N431,32). This rod-like
grains provide in-situ toughening mechanism to Si3N4 Radiopacity evaluation
ceramic. Deflection of the crack along the boundaries of Dentin and Al have equal radiopacity and the radiopacity
these specific grains, bridging of a propagating crack or of enamel is nearly twice than the radiopacity of Al with
pulling-out are the mechanisms to reduce the energy of the same thickness values37). This study showed that
crack and provide higher fracture toughness compare to radiointensity of Si3N4 was only slightly higher than Al,
other ceramics33). indicating that the radiopacity of Si3N4 is comparable
The strength of the ZrO2 samples was also lower to that of dentin. Lower radiointensity means partial
than the values reported in the literature. The test was radiolucent behavior. This provides a significant
conducted according to standard used for advanced advantage for a dental material in post-operative
ceramics. The mechanical characterization of dental process. The low radiopacity of Si3N4 will enable for both
materials is done according to the ISO 6872 standards, the restoration and the surrounding tissues to be imaged
where smaller specimens are used. The probability of using plain radiography19).
finding a bigger flaw or more number of defects in a
larger ceramic body is higher compared to smaller size. CONCLUSION
This size difference can be the reason of observed lower
strength of ZrO2. Up to now, it has been accepted that the dark-gray
Hardness is another critical mechanical property color of dense Si3N4 ceramics limits their application
in restorative materials. The lower hardness of Si3N4 in restorative dentistry. This study investigated the
compared to ZrO2 is an important benefit for restorative potential use of porous Si3N4 for all ceramic dental
applications. As the hardness difference between the restorations as a core material and results were
enamel and the restorative material becomes higher, compared with a commercial ZrO2 ceramic. Some critical
wear related problems can be experienced in the opposing parameters were characterized to show the benefits
natural tooth29). of Si3N4 as a dental restorative ceramic. The color of
Si3N4 was tailored by the porosity introduced and a
Color shade of samples color shade suitable for restorative applications was
The optical properties are an important aspect of dental obtained. The flexural strength of Si3N4 was measured
restorative materials. The color shade of the materials as 418 MPa despite the open porosity content of nearly
depends on many variables, such as, crystal morphology, 10.54%. The hardness of Si3N4 was 10.9 MPa whereas
grain size, grain boundary, porosity, etc. For industrial ZrO2 had 13.7 MPa, which reduces the risk for wearing
applications of Si3N4, the material is usually produced in of natural teeth compared to ZrO2. Shear bond strength
a dense form. (Testing of silicon nitride ceramic bearings test indicated that the usage of coupling agent for Si3N4
for total hip arthroplasty) The shade of the dense Si3N4 is essential. When coupling agent was used, Si3N4 had
is relatively dark, gray, sometimes close to black. This similar shear bond strength to ZrO2. The radiolucent
1086 Dent Mater J 2020; 39(6): 1080–1086
behavior of Si3N4 shown here will enable for both the W, et al. Silicon nitride bioceramics induce chemically driven
restorations and the surrounding tissues to be imaged lysis in porphyromonas gingivalis. Langmuir 2016; 32: 3024-
3035.
using plain radiography. The results of this study show
19) Badran Z, Struillou X, Hughes FJ, Soueidan A, Hoornaert A,
that with tailored manufacturing methods, Si3N4 can be Ide M. Silicon nitride (Si3N4) implants: the future of dental
considered as a dental restorative material. implantology? J Oral Implantol 2017; 43: 240-244.
20) Herrmann M, Goeb O. Colour of gas-pressure-sintered silicon
nitride ceramics Part I. Experimental data. J Europ Ceram
REFERENCES Soc 2001; 21: 303-314.
1) Duraccio D, Mussano F, Faga MG. Biomaterials for dental 21) Standard Test Methods for Apparent Porosity, Water
implants: current and future trends. J Mater Sci 2015; 50: Absorption, Apparent Specific Gravity, and Bulk Density
4779-4812. of Burned Refractory Brick and Shapes by Boiling Water,
2) Della Bona A, Pecho OE, Alessandretti R. Zirconia as a dental American Society for Testing and Materials; 2015.
biomaterial. Mater 2015; 8: 4978-4991. 22) Standard test method for flexural strength of advanced
3) Zhang Y, Lawn BR. Novel zirconia materials in dentistry. J ceramics at ambient temperature: American Society for
Dent Res 2018; 97: 140-147. Testing and Materials; 2003.
4) Guazzato M, Albakry M, Ringer SP, Swain MV. Strength, 23) Wadhwani C, Hess T, Faber T, Piñeyro A, Chen CS. A
fracture toughness and microstructure of a selection of all- descriptive study of the radiographic density of implant
ceramic materials. Part II. Zirconia-based dental ceramics. restorative cements. J Prosthet Dent 2010; 103: 295-302.
Dent Mater 2004; 20: 449-456. 24) Paravina RD, Powers JM, Fay RM. Dental color standards:
5) Daou EE. The zirconia ceramic: strengths and weaknesses. shade tab arrangement. J Esthet Restor Dent 2001; 13: 254-
Open Dent J 2014; 18: 33-42. 263.
6) McEntire B, Lakshminarayanan R, Ray D, Clarke I, 25) Karunaratne B, Lumby R, Lewis M. Rare-earth-doped α′-
Puppulin L, Pezzotti G. Silicon nitride bearings for total joint Sialon ceramics with novel optical properties. J Mater Res
arthroplasty. Lubricants 2016; 4: 35. 1996; 11: 2790-2794.
7) Rahaman M, Xiao W. Silicon nitride bioceramics in healthcare. 26) Plucknett KP, Quinlan M, Garrido L, Genova L.
Int J Appl Ceram Technol 2018; 15: 861-872. Microstructural development in porous β-Si3N4 ceramics
8) Howlett C, McCartney E, Ching W. The effect of silicon prepared with low volume RE2O3–MgO–(CaO) additions
nitride ceramic on rabbit skeletal cells and tissue. An in vitro (RE=La, Nd, Y, Yb). Mater Sci Eng A 2008; 489: 337-350.
and in vivo investigation. Clin Orthop Relat Res 1989; 244: 27) Yang J-F, Deng Z-Y, Ohji T. Fabrication and characterisation
293-304. of porous silicon nitride ceramics using Yb2O3 as sintering
9) Salgueiredo E, Vila M, Silva M, Lopes M, Santos J, Costa additive. J Europ Ceram Soc 2003; 23: 371-378.
F, et al. Biocompatibility evaluation of DLC-coated Si3N4 28) German RM. Coarsening in sintering: grain shape distribution,
substrates for biomedical applications. Diam Relat Mater grain size distribution, and grain growth kinetics in solid-pore
2008; 17: 878-881. systems. Crit Rev Solid State Mater Sci 2010; 35: 263-305.
10) Watts D, McCabe J. Aluminium radiopacity standards for 29) Ban S. Reliability and properties of core materials for all-
dentistry: an international survey. J Dent 1999; 27: 73-78. ceramic dental restorations. Jpn Dent Sci Rev 2008; 44:
11) Pekkan G, Pekkan K, Hatipoglu MG, Tuna SH. Comparative 3-21.
radiopacity of ceramics and metals with human and bovine 30) Richerson DW. Modern ceramic engineering: properties,
dental tissues. J Prosthet Dent 2011; 106: 109-117. processing, and use in design: CRC press; 2005.
12) Ghalme S, Falak Y. Review on evolution of silicon nitride 31) Chen W, Lv Z, Gao D, Ai X. Study on preparation and physical
in the field of orthopedics. Current Trends in Biomedical mechanical properties of Si3N4 composite ceramics. MATEC
Engineering & Biosciences (CTBEB). 2018;11:3. Web of Conferences 2015; 22: 05019.
13) Bock RM, McEntire BJ, Bal BS, Rahaman MN, Boffelli M, 32) Kawai C, Yamakawa A. Effect of porosity and microstructure
Pezzotti G. Surface modulation of silicon nitride ceramics for on the strength of Si3N4: designed microstructure for high
orthopaedic applications. Acta Biomater 2015; 26: 318-330. strength, high thermal shock resistance, and facile machining.
14) Vogler EA. Water and the acute biological response to J Am Ceram Soc 1997; 80: 2705-2708.
surfaces. J Biomater Sci Polym Ed. 1999; 10: 1015-1045. 33) Bal BS, Rahaman MN. Orthopedic applications of silicon
15) Gorth DJ, Puckett S, Ercan B, Webster TJ, Rahaman M, Bal nitride ceramics. Acta Biomater 2012; 8: 2889-2898
BS. Decreased bacteria activity on Si3N4 surfaces compared 34) Nagaoka N, Yoshihara K, Feitosa VP, Tamada Y, Irie M,
with PEEK or titanium. Int J Nanomedicine 2012; 7: 4829. Yoshida Y, et al. Chemical interaction mechanism of 10-MDP
16) Ishikawa M, de Mesy Bentley KL, McEntire BJ, Bal BS, with zirconia. Sci Rep 2017; 7: 455-463.
Schwarz EM, Xie C. Surface topography of silicon nitride 35) Lung CYK, Matinlinna JP. Aspects of silane coupling agents
affects antimicrobial and osseointegrative properties of tibial and surface conditioning in dentistry: an overview. Dent
implants in a murine model. J Biomed Mater Res Part A Mater 2012; 28: 467-477.
2017; 105: 3413-3421. 36) Alex G. Universal adhesives: the next evolution in adhesive
17) Webster TJ, Patel AA, Rahaman M, Bal BS. Anti-infective dentistry. Compend Contin Educ Dent 2015; 36: 15-26.
and osteointegration properties of silicon nitride, poly (ether 37) Ergücü Z, Türkün L, Önem E, Güneri P. Comparative
ether ketone), and titanium implants. Acta Biomater 2012; 8: radiopacity of six flowable resin composites. Oper Dent 2010;
4447-4454. 35: 436-440.
18) Pezzotti G, Bock RM, McEntire BJ, Jones E, Boffelli M, Zhu